Composite ionic surfactant

Abstract

The invention relates to the technical field of oil exploitation, and discloses a composite ionic surfactant which is prepared by the following steps: mixing vacuum residue and sulfur trioxide for sulfonation reaction, aging when the reaction temperature is not increased any more, adding isopropanol, uniformly stirring, and adding a sodium hydroxide solution for neutralization reaction to obtain residue sulfonate; the preparation method comprises the following steps: mixing fatty alcohol-polyoxyethylene ether, acrylic acid and maleic anhydride for reaction to obtain modified fatty alcohol-polyoxyethylene ether; the preparation method comprises the following steps: mixing residual oil sulfonate, modified fatty alcohol-polyoxyethylene ether and a reinforcing agent, heating, adding a plasticizer, linear heavy alkyl benzene sulfonic acid and water, continuously stirring, cooling and discharging to obtain the composite ionic surfactant. And residual oil sulfonate and reinforcing agent molecules are fixed in a network, so that disordered aggregation is reduced, and the salt resistance is improved.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum exploitation, in particular to a composite ionic surfactant. Background Art

[0002] Various chemical flooding technologies involving surfactants are widely used in tertiary oil recovery, such as ASP flooding, binary flooding and surfactant flooding. Surfactants can improve oil recovery by reducing oil-water interfacial tension and increasing capillary number. For example, petroleum sulfonates and alkylbenzene sulfonates can be compatible with formation fluids to form ultra-low interfacial tension, thereby improving oil recovery. Among them, petroleum sulfonates are anionic surfactants synthesized from petroleum distillates or crude oil. The main component is monosulfonates of aromatic compounds, which have a similar molecular equivalent to crude oil and are widely used as surfactants in enhanced oil recovery technology.

[0003] However, petroleum sulfonates have the disadvantage of poor salt resistance. During the oil recovery process, petroleum sulfonates easily react with multivalent metal cations in the formation to form precipitates, resulting in the loss of surfactants. The generated precipitates will also block the rock pores and reduce the performance of the surfactant oil recovery system. In addition, during the oil recovery process of petroleum sulfonate surfactants in high-temperature oil reservoirs, the structure of the petroleum sulfonates is easily destroyed or changed, affecting the crude oil recovery rate. Summary of the invention

[0004] The invention provides a composite ionic surfactant, which solves the problem of poor salt resistance and temperature resistance of petroleum sulfonate surfactant.

[0005] The technical solution of the present invention: A method for preparing a composite ionic surfactant is prepared by the following method: S1. Vacuum residue oil and sulfur trioxide are mixed for sulfonation reaction. When the reaction temperature is no longer increased, aging is performed, isopropanol is added, stirred evenly, and sodium hydroxide solution is added for neutralization reaction to obtain residue oil sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer are mixed, heated to 40-50 ° C, a plasticizer, a linear heavy alkylbenzene sulfonic acid and water are added, stirring is continued for 45-55min, the temperature is lowered and the material is discharged to obtain a composite ionic surfactant; The reinforcing agent is obtained by mixing and reacting nanoparticles modified with sulfonated lignin, biphenyl, a catalyst and dichloromethane, and then surface-modifying with polydopamine; The sulfonated lignin modified nanoparticles are obtained by reacting lignin, a coupling agent and nanoparticles in a mixed manner, and then reacting the mixture with formaldehyde and anhydrous sodium sulfite for sulfomethylation.

[0006] Furthermore, in step S1, the sulfonation reaction temperature is 40-50°C, and the sulfonation reaction time is when the reaction temperature no longer increases.

[0007] Furthermore, in step S1, the aging temperature is 40-50°C, and the aging time is 1-2h.

[0008] Furthermore, in step S1, the neutralization reaction temperature is 50-55° C., and the neutralization reaction time is 1-2 h.

[0009] Furthermore, in step S1, the mass fraction of the sodium hydroxide solution is 25-35%.

[0010] Furthermore, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is (50-60):(5-10):(8-10):(15-20).

[0011] Furthermore, in step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, reinforcing agent, plasticizer, linear heavy alkylbenzene sulfonic acid and water is (70-80):(10-15):(5-8):(0.5-0.7):(2-4):(10-15).

[0012] Further, the modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. Mix fatty alcohol polyoxyethylene ether and acrylic acid, stir evenly, add p-toluenesulfonic acid and hydroquinone, maintain vacuum, react at 85-95 ° C for 5-7h, increase vacuum to remove unreacted acrylic acid, and obtain fatty alcohol polyoxyethylene ether acrylate; A2. Add fatty alcohol polyoxyethylene ether acrylate and ammonium persulfate to deionized water, stir evenly, add maleic anhydride, stir and react at 50-60°C for 10-20 minutes, cool to room temperature, add hydroquinone to stop the reaction, and obtain modified fatty alcohol polyoxyethylene ether.

[0013] Furthermore, in the above reaction process A1, p-toluenesulfonic acid is used as a catalyst, and the fatty alcohol polyoxyethylene ether and acrylic acid undergo an esterification reaction, so that acrylic acid is grafted onto the fatty alcohol polyoxyethylene ether molecular chain, giving a reactive double bond, and obtaining fatty alcohol polyoxyethylene ether acrylate.

[0014] Furthermore, in the above reaction process A2, ammonium persulfate is used as an initiator, and maleic anhydride can react with the double bonds in the fatty alcohol polyoxyethylene ether acrylate, so that the maleic anhydride is grafted on the fatty alcohol polyoxyethylene ether acrylate to obtain modified fatty alcohol polyoxyethylene ether.

[0015] Furthermore, in step A1, the mass ratio of the fatty alcohol polyoxyethylene ether, acrylic acid, p-toluenesulfonic acid and hydroquinone is (25-35):(4-5):(1.1-1.3):(0.02-0.04).

[0016] Furthermore, in step A2, the mass ratio of the fatty alcohol polyoxyethylene ether acrylate, ammonium persulfate, deionized water, maleic anhydride and hydroquinone is (25-35):(0.03-0.07):(25-35):(8-9):(0.01-0.03).

[0017] Furthermore, the enhancer is specifically prepared by the following steps: B1. Add the nanoparticles to ethanol and deionized water, stir evenly, add the coupling agent and sodium hydroxide solution, stir and react at 75-85°C for 1-2h, add lignin, continue stirring and reacting for 1-2h, cool to room temperature, filter, wash, and dry to obtain lignin-modified nanoparticles; B2. Add lignin-modified nanoparticles to deionized water, stir evenly, heat to 45-50°C, add sodium hydroxide solution to adjust the pH to 8-9, pass formaldehyde and anhydrous sodium sulfite, stir to react for 2-4h, cool to room temperature, filter, wash, and dry to obtain sulfonated lignin-modified nanoparticles; B3. Add the catalyst and biphenyl to dichloromethane, stir evenly, add the sulfonated lignin-modified nanoparticles, stir evenly, introduce nitrogen, stir at low temperature for 3-5h, stir at 25-35°C for 7-9h, stir at 35-45°C for 11-13h, stir at 55-65°C for 11-13h, stir at 75-85°C for 22-24h, add hydrochloric acid solution to terminate the reaction, filter, wash, extract, and dry to obtain a composite layered porous polymer; B4. Add the composite layered porous polymer to deionized water, stir evenly, add Tris-HCl buffer, stir evenly, add dopamine, stir and react at 30-40°C for 1-2h, filter, wash and dry to obtain an enhancer.

[0018] Furthermore, during the above-mentioned B1 reaction, the hydroxyl groups generated by the hydrolysis of the coupling agent can be chemically bonded to the hydroxyl groups on the surface of the nanoparticles, and the amino groups contained in the coupling agent can be chemically bonded to the phenolic hydroxyl groups contained in the lignin, so that the lignin is coated on the surface of the nanoparticles to obtain lignin-modified nanoparticles.

[0019] Furthermore, in the above-mentioned B2 reaction process, formaldehyde and sodium sulfite generate hydroxymethyl sulfonate under alkaline conditions, and the hydroxymethyl sulfonate reacts with lignin on the surface of the lignin-modified nanoparticles to achieve sulfonation modification of the lignin-modified nanoparticles.

[0020] Furthermore, in the above-mentioned B3 reaction process, aluminum chloride is used as a catalyst and dichloromethane is used as a solvent. At low temperature, dichloromethane can react with biphenyl to undergo a Friedel-Crafts reaction to form a chloroalkyl-substituted aromatic monomer. As the reaction proceeds, the chloroalkyl-substituted aromatic monomer is bridged and stacked to form a layered porous network polymer. During the reaction, biphenyl can interact with lignin on the surface of the modified nanoparticles through the benzene ring, so that the modified nanoparticles are embedded in the layered porous network polymer to obtain a composite layered porous polymer.

[0021] Furthermore, during the above B4 reaction, in the Tris-HCl buffer, dopamine can self-polymerize on the surface of the composite layered porous polymer to form polydopamine, thereby forming a polydopamine-modified composite layered porous polymer as an enhancer.

[0022] Furthermore, in step B1, the ratio of the nanoparticles, ethanol, deionized water, coupling agent, sodium hydroxide solution and lignin is (1.1-1.3) g: (90-100) mL: (4-6) mL: (0.3-0.7) g: (4-6) mL: (0.4-0.6) g.

[0023] Furthermore, in step B2, the ratio of the lignin-modified nanoparticles, deionized water, formaldehyde and anhydrous sodium sulfite is (2-3) g: (70-90) mL: (0.2-0.4) mL: (1.6-2) g.

[0024] Furthermore, in step B3, the amount ratio of the catalyst, biphenyl, dichloromethane, sulfonated lignin-modified nanoparticles and hydrochloric acid solution is (2-3) g: (0.6-1) g: (8-12) mL: (0.2-0.4) g: (1-2) mL.

[0025] Furthermore, in step B4, the ratio of the composite layered porous polymer, deionized water, Tris-HCl buffer and dopamine is (1.5-1.7) g: (90-110) mL: (0.7-0.9) g: (0.6-0.8) g.

[0026] Furthermore, the nanoparticles are selected from any one of nano-silicon dioxide, nano-aluminum oxide, and nano-magnesium oxide.

[0027] The present invention has the following beneficial effects: (1) In the technical solution of the present invention, lignin is coated on the surface of nanoparticles through a coupling agent. On the one hand, the phenolic hydroxyl groups contained in lignin can serve as complexing sites for metal salt ions in formation water, thereby preventing residual oil sulfonates from reacting with multivalent metal cations in the formation to form precipitation, which leads to the loss of surfactants. On the other hand, nanoparticles, as inorganic materials, have excellent heat resistance and are dispersed in residual oil sulfonates, which can enhance the heat resistance of residual oil sulfonates. The prepared composite ionic surfactant has excellent heat resistance, thereby avoiding oil displacement in high-temperature reservoirs, where the structure of residual oil sulfonates is easily destroyed or changed, which affects the original Oil recovery rate. In addition, the lignin-modified nanoparticles contain a large number of benzene ring structures, which are conducive to the embedding of the lignin-modified nanoparticles into the porous polymer, thereby increasing the interlayer spacing and pore structure of the porous polymer, improving the adsorption of multivalent metal cations in the formation, and enhancing the salt resistance of the residual oil sulfonate; the sulfomethylation treatment of the lignin-modified nanoparticles improves the compatibility of the lignin-modified nanoparticles with the residual oil sulfonate, so that the lignin-modified nanoparticles are better dispersed in the residual oil sulfonate surfactant system, thereby improving the crude oil recovery rate, and the introduction of sulfonic acid groups further enhances the adsorption of multivalent metal cations in the formation.

[0028] (2) In the technical scheme of the present invention, nanoparticles modified with sulfonated lignin, biphenyl, a catalyst and dichloromethane are mixed and reacted to form a composite layered porous polymer. On the one hand, a Friedel-Crafts reaction occurs on the surface of the nanoparticles modified with sulfonated lignin, which can increase the interlayer spacing of the layered porous network polymer, improve the adsorption of polyvalent metal cations in the formation, and enhance the salt resistance of the residual oil sulfonate. The formed layered porous network polymer has excellent temperature resistance, which improves the high temperature resistance of the residual oil sulfonate and improves the oil recovery efficiency. On the other hand, the nanoparticles modified with sulfonated lignin interact with the layered porous network polymer through the benzene ring, thereby increasing the crosslinking density, improving the porosity, and enhancing the adsorption efficiency of the polyvalent metal cations in the formation.

[0029] (3) In the technical scheme of the present invention, the composite layered porous polymer is surface-modified with polydopamine as an enhancer, so that the surface of the composite porous material carries a large number of phenolic hydroxyl groups, further improving the adsorption of multivalent metal cations in the formation. After the composite porous material is surface-modified with polydopamine, it is beneficial for the composite layered porous polymer to be dispersed in the residual oil sulfonate, thereby improving the salt resistance and temperature resistance of the residual oil sulfonate. In addition, the enhancer serves as a bridge between the non-ionic surfactant fatty alcohol polyoxyethylene ether and the residual oil sulfonate, thereby improving the compatibility of the non-ionic surfactant fatty alcohol polyoxyethylene ether and the residual oil sulfonate and improving the stability of the composite ionic surfactant.

[0030] (4) In the technical scheme of the present invention, fatty alcohol polyoxyethylene ether reacts with acrylic acid, so that acrylic acid is grafted onto the fatty alcohol polyoxyethylene ether molecular chain, giving a reactive double bond, which is conducive to introducing hydrophilic groups into the fatty alcohol polyoxyethylene ether molecular chain, improving the compatibility of the nonionic surfactant fatty alcohol polyoxyethylene ether with residual oil sulfonate, and the hydrophobic fatty chain of the fatty alcohol polyoxyethylene ether is adsorbed on the oil phase, and the hydrophilic polyoxyethylene chain extends into the water phase to form a directional arrangement, which significantly reduces the oil-water interfacial tension, reduces the adhesion between crude oil and rock, promotes the peeling of residual oil droplets from the pore surface, and improves the displacement efficiency. Maleic anhydride is grafted onto fatty alcohol polyoxyethylene ether acrylate. On the one hand, the carboxyl group generated by the ring-opening of maleic anhydride provides a hydrophilic carboxyl group, thereby improving the compatibility of fatty alcohol polyoxyethylene ether with residual oil sulfonate. On the other hand, the carboxyl group contained can combine with the phenolic hydroxyl group in the enhancer, and can form a cross-linked network structure in the composite ionic surfactant system, thereby enhancing the steric hindrance of the composite ionic surfactant. In addition, the residual oil sulfonate and enhancer molecules are fixed in the network, thereby reducing disordered aggregation. The sulfonic acid group is fixed in the network, and high-valent ions cannot effectively shield charges, thereby improving salt resistance. DETAILED DESCRIPTION

[0031] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] The raw materials used in the examples of the present invention are as follows, and all reagents used are of analytical grade.

[0033] Among them, the density of vacuum residue oil is 0.88g / cm 2 , the solidification point is 22.1℃, the boiling point is 550℃, and the kinematic viscosity at 45℃ is 17683.91mm 2 / s, 50℃ kinematic viscosity is 4553.84mm 2 / s.

[0034] The plasticizer was epoxidized soybean oil with an epoxide value of 6.23%, analytically pure, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0035] Linear heavy alkylbenzene sulfonic acid was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.

[0036] Fatty alcohol polyoxyethylene ether was purchased from Guangzhou Suixin Chemical Co., Ltd.

[0037] The nanoparticles are nano-silicon dioxide with a particle size of 50nm.

[0038] The coupling agent is γ-aminopropyltriethoxysilane.

[0039] The catalyst is aluminum chloride; the biphenyl is N,N,N',N'-tetraphenylbenzidine.

[0040] Example 1 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 40°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 40°C for aging for 1h, add isopropanol, stir evenly, add 25% sodium hydroxide solution by mass, and neutralize at 50°C for 1h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 40 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 45 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 50:5:8:15; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water is 70:10:5:0.5:2:10.

[0041] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 25g of fatty alcohol polyoxyethylene ether and 4g of acrylic acid were mixed and stirred evenly, 1.1g of p-toluenesulfonic acid and 0.02g of hydroquinone were added, and the vacuum degree was maintained at 0.03MPa. After reacting at 85°C for 5h, the vacuum degree was increased to remove unreacted acrylic acid to obtain fatty alcohol polyoxyethylene ether acrylate; A2. Add 25g of fatty alcohol polyoxyethylene ether acrylate and 0.03g of ammonium persulfate to 25g of deionized water, stir evenly, add 8g of maleic anhydride, stir and react at 50°C for 10min, cool to room temperature, add 0.01g of hydroquinone to stop the reaction, and obtain modified fatty alcohol polyoxyethylene ether.

[0042] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.1 g of nano-silica to 90 mL of ethanol and 4 mL of deionized water, stir evenly, add 0.3 g of γ-aminopropyltriethoxysilane and 4 mL of 30% sodium hydroxide solution, stir and react at 75 °C for 1 h, add 0.4 g of lignin, continue stirring and reacting for 1 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain lignin-modified nano-silica; B2. Add 2 g of lignin-modified nano-silica to 70 mL of deionized water, stir evenly, heat to 45 °C, add 10% sodium hydroxide solution to adjust the pH to 8, pass 0.2 mL of formaldehyde and 1.6 g of anhydrous sodium sulfite, stir and react for 2 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain sulfonated lignin-modified nano-silica; B3. Add 2g aluminum chloride and 0.6g N,N,N',N'-tetraphenylbenzidine to 8mL dichloromethane, stir evenly, add 0.2g sulfonated lignin-modified nano-silica, stir evenly, introduce nitrogen, stir at 0°C for 3h, stir at 25°C for 7h, stir at 35°C for 11h, stir at 55°C for 13h, stir at 75°C for 22h, add 1mL of 0.6mol / L hydrochloric acid solution to terminate the reaction, filter, wash with deionized water 3 times, wash with ethanol 2 times, extract with ethanol for 48h, and dry in an oven at 65°C for 24h to obtain a composite layered porous polymer; B4. Add 1.5 g of the composite layered porous polymer to 90 mL of deionized water, stir evenly, add 0.7 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.6 g of dopamine, stir and react at 30°C for 1 hour, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 hours to obtain an enhancer.

[0043] Example 2 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 45°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 45°C for aging for 1.5h, add isopropanol, stir evenly, add 30% sodium hydroxide solution by mass, and neutralize at 53°C for 1.5h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 45 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 50 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 55:8:9:18; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 75:13:7:0.6:3:13.

[0044] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 30g of fatty alcohol polyoxyethylene ether and 4.5g of acrylic acid were mixed and stirred evenly, 1.2g of p-toluenesulfonic acid and 0.03g of hydroquinone were added, and the vacuum degree was maintained at 0.03MPa. After reacting at 90°C for 6h, the vacuum degree was increased to remove unreacted acrylic acid to obtain fatty alcohol polyoxyethylene ether acrylate; A2. Add 20 g of fatty alcohol polyoxyethylene ether acrylate and 0.05 g of ammonium persulfate to 30 g of deionized water, stir evenly, add 8.5 g of maleic anhydride, stir and react at 55 ° C for 15 min, cool to room temperature, add 0.02 g of hydroquinone to stop the reaction, and obtain modified fatty alcohol polyoxyethylene ether.

[0045] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.2 g of nano-silica to 95 mL of ethanol and 5 mL of deionized water, stir evenly, add 0.5 g of γ-aminopropyltriethoxysilane and 5 mL of 30% sodium hydroxide solution, stir and react at 80 ° C for 1.5 h, add 0.5 g of lignin, continue to stir and react for 1.5 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 ° C for 10 min to obtain lignin-modified nano-silica; B2. Add 2.5 g of lignin-modified nano-silica to 80 mL of deionized water, stir evenly, heat to 48 °C, add 10% sodium hydroxide solution to adjust the pH to 8.5, pass 0.3 mL of formaldehyde and 1.8 g of anhydrous sodium sulfite, stir and react for 3 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain sulfonated lignin-modified nano-silica; B3. Add 2.5g aluminum chloride and 0.8g N,N,N',N'-tetraphenylbenzidine to 10mL dichloromethane, stir evenly, add 0.3g sulfonated lignin-modified nano-silica, stir evenly, introduce nitrogen, stir at 0.5°C for 4h, stir at 30°C for 8h, stir at 40°C for 12h, stir at 60°C for 12h, stir at 80°C for 23h, add 1.5mL of 0.6mol / L hydrochloric acid solution to terminate the reaction, filter, wash with deionized water 3 times, wash with ethanol 2 times, extract with ethanol for 48h, and dry in an oven at 65°C for 24h to obtain a composite layered porous polymer; B4. Add 1.6 g of the composite layered porous polymer to 100 mL of deionized water, stir evenly, add 0.8 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.7 g of dopamine, stir and react at 35°C for 1.5 h, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 h to obtain an enhancer.

[0046] Example 3 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 50°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 50°C for aging for 2h, add isopropanol, stir evenly, add 35% sodium hydroxide solution by mass, and neutralize at 55°C for 2h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 50 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 55 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 60:10:10:20; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 80:15:8:0.7:4:15.

[0047] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 35g of fatty alcohol polyoxyethylene ether and 5g of acrylic acid were mixed and stirred evenly, 1.3g of p-toluenesulfonic acid and 0.04g of hydroquinone were added, and the vacuum degree was maintained at 0.03MPa. After reacting at 95°C for 7h, the vacuum degree was increased to remove unreacted acrylic acid to obtain fatty alcohol polyoxyethylene ether acrylate; A2. 25 g of fatty alcohol polyoxyethylene ether acrylate and 0.07 g of ammonium persulfate were added to 35 g of deionized water, stirred evenly, 9 g of maleic anhydride was added, stirred and reacted at 60 ° C for 20 min, cooled to room temperature, and 0.03 g of hydroquinone was added to stop the reaction to obtain modified fatty alcohol polyoxyethylene ether.

[0048] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.3 g of nano-silica to 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 0.7 g of γ-aminopropyltriethoxysilane and 6 mL of 30% sodium hydroxide solution, stir and react at 85 °C for 2 h, add 0.6 g of lignin, continue stirring and reacting for 2 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain lignin-modified nano-silica; B2. Add 3 g of lignin-modified nano-silica to 90 mL of deionized water, stir evenly, heat to 50 °C, add 10% sodium hydroxide solution to adjust the pH to 9, pass 0.4 mL of formaldehyde and 2 g of anhydrous sodium sulfite, stir and react for 4 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain sulfonated lignin-modified nano-silica; B3. Add 3g aluminum chloride and 1g N,N,N',N'-tetraphenylbenzidine to 12mL dichloromethane, stir evenly, add 0.4g sulfonated lignin-modified nano-silica, stir evenly, introduce nitrogen, stir at 1°C for 5h, stir at 35°C for 9h, stir at 45°C for 13h, stir at 65°C for 13h, stir at 85°C for 24h, add 2mL of 0.6mol / L hydrochloric acid solution to terminate the reaction, filter, wash with deionized water 3 times, wash with ethanol 2 times, extract with ethanol for 48h, and dry in an oven at 65°C for 24h to obtain a composite layered porous polymer; B4. Add 1.7 g of the composite layered porous polymer to 110 mL of deionized water, stir evenly, add 0.9 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.8 g of dopamine, stir and react at 40°C for 2 h, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 h to obtain an enhancer.

[0049] Comparative Example 1 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 50°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 50°C for aging for 2h, add isopropanol, stir evenly, add 35% sodium hydroxide solution by mass, and neutralize at 55°C for 2h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 50 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 55 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 60:10:10:20; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 80:15:8:0.7:4:15.

[0050] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: Add 25 g of fatty alcohol polyoxyethylene ether and 0.07 g of ammonium persulfate to 35 g of deionized water, stir evenly, add 9 g of maleic anhydride, stir and react at 60° C. for 20 min, cool to room temperature, add 0.03 g of hydroquinone to stop the reaction, and obtain modified fatty alcohol polyoxyethylene ether.

[0051] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.3 g of nano-silica to 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 0.7 g of γ-aminopropyltriethoxysilane and 6 mL of 30% sodium hydroxide solution, stir and react at 85 °C for 2 h, add 0.6 g of lignin, continue stirring and reacting for 2 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain lignin-modified nano-silica; B2. Add 3 g of lignin-modified nano-silica to 90 mL of deionized water, stir evenly, heat to 50 °C, add 10% sodium hydroxide solution to adjust the pH to 9, pass 0.4 mL of formaldehyde and 2 g of anhydrous sodium sulfite, stir and react for 4 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain sulfonated lignin-modified nano-silica; B3. Add 3g aluminum chloride and 1g N,N,N',N'-tetraphenylbenzidine to 12mL dichloromethane, stir evenly, add 0.4g sulfonated lignin-modified nano-silica, stir evenly, introduce nitrogen, stir at 1°C for 5h, stir at 35°C for 9h, stir at 45°C for 13h, stir at 65°C for 13h, stir at 85°C for 24h, add 2mL of 0.6mol / L hydrochloric acid solution to terminate the reaction, filter, wash with deionized water 3 times, wash with ethanol 2 times, extract with ethanol for 48h, and dry in an oven at 65°C for 24h to obtain a composite layered porous polymer; B4. Add 1.7 g of the composite layered porous polymer to 110 mL of deionized water, stir evenly, add 0.9 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.8 g of dopamine, stir and react at 40°C for 2 h, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 h to obtain an enhancer.

[0052] Comparative Example 2 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 50°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 50°C for aging for 2h, add isopropanol, stir evenly, add 35% sodium hydroxide solution by mass, and neutralize at 55°C for 2h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether and acrylic acid are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 50 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 55 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 60:10:10:20; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 80:15:8:0.7:4:15.

[0053] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 35g of fatty alcohol polyoxyethylene ether and 5g of acrylic acid were mixed and stirred evenly. 1.3g of p-toluenesulfonic acid and 0.04g of hydroquinone were added. The vacuum degree was maintained at 0.03MPa. After reacting at 95°C for 7h, the vacuum degree was increased to remove unreacted acrylic acid to obtain modified fatty alcohol polyoxyethylene ether.

[0054] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.3 g of nano-silica to 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 0.7 g of γ-aminopropyltriethoxysilane and 6 mL of 30% sodium hydroxide solution, stir and react at 85 °C for 2 h, add 0.6 g of lignin, continue stirring and reacting for 2 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain lignin-modified nano-silica; B2. Add 3 g of lignin-modified nano-silica to 90 mL of deionized water, stir evenly, heat to 50 °C, add 10% sodium hydroxide solution to adjust the pH to 9, pass 0.4 mL of formaldehyde and 2 g of anhydrous sodium sulfite, stir and react for 4 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain sulfonated lignin-modified nano-silica; B3. Add 3g aluminum chloride and 1g N,N,N',N'-tetraphenylbenzidine to 12mL dichloromethane, stir evenly, add 0.4g sulfonated lignin-modified nano-silica, stir evenly, introduce nitrogen, stir at 1°C for 5h, stir at 35°C for 9h, stir at 45°C for 13h, stir at 65°C for 13h, stir at 85°C for 24h, add 2mL of 0.6mol / L hydrochloric acid solution to terminate the reaction, filter, wash with deionized water 3 times, wash with ethanol 2 times, extract with ethanol for 48h, and dry in an oven at 65°C for 24h to obtain a composite layered porous polymer; B4. Add 1.7 g of the composite layered porous polymer to 110 mL of deionized water, stir evenly, add 0.9 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.8 g of dopamine, stir and react at 40°C for 2 h, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 h to obtain an enhancer.

[0055] Comparative Example 3 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 50°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 50°C for aging for 2h, add isopropanol, stir evenly, add 35% sodium hydroxide solution by mass, and neutralize at 55°C for 2h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 50 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 55 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 60:10:10:20; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 80:15:8:0.7:4:15.

[0056] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 35g of fatty alcohol polyoxyethylene ether and 5g of acrylic acid were mixed and stirred evenly, 1.3g of p-toluenesulfonic acid and 0.04g of hydroquinone were added, and the vacuum degree was maintained at 0.03MPa. After reacting at 95°C for 7h, the vacuum degree was increased to remove unreacted acrylic acid to obtain fatty alcohol polyoxyethylene ether acrylate; A2. 25 g of fatty alcohol polyoxyethylene ether acrylate and 0.07 g of ammonium persulfate were added to 35 g of deionized water, stirred evenly, 9 g of maleic anhydride was added, stirred and reacted at 60 ° C for 20 min, cooled to room temperature, and 0.03 g of hydroquinone was added to stop the reaction to obtain modified fatty alcohol polyoxyethylene ether.

[0057] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.3 g of nano-silica to 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 0.6 g of lignin, continue stirring and reacting for 2 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 ° C for 10 min to obtain a mixture; B2. Add 3 g of the mixture to 90 mL of deionized water, stir evenly, heat to 50 ° C, add 10% sodium hydroxide solution to adjust the pH to 9, pass 0.4 mL of formaldehyde and 2 g of anhydrous sodium sulfite, stir and react for 4 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 ° C for 10 min to obtain a sulfonated mixture; B3. Add 3 g of aluminum chloride and 1 g of N,N,N',N'-tetraphenylbenzidine to 12 mL of dichloromethane, stir evenly, add 0.4 g of the sulfonated mixture, stir evenly, introduce nitrogen, stir at 1 ° C for 5 h, stir at 35 ° C for 9 h, stir at 45 ° C for 13 h, stir at 65 ° C for 13 h, stir at 85 ° C for 24 h, add 2 mL of 0.6 mol / L hydrochloric acid solution to terminate the reaction, filter, wash with deionized water 3 times, wash with ethanol 2 times, extract with ethanol for 48 h, and dry in an oven at 65 ° C for 24 h to obtain a composite layered porous polymer; B4. Add 1.7 g of the composite layered porous polymer to 110 mL of deionized water, stir evenly, add 0.9 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.8 g of dopamine, stir and react at 40°C for 2 h, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 h to obtain an enhancer.

[0058] Comparative Example 4 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 50°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 50°C for aging for 2h, add isopropanol, stir evenly, add 35% sodium hydroxide solution by mass, and neutralize at 55°C for 2h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 50 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 55 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 60:10:10:20; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 80:15:8:0.7:4:15.

[0059] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 35g of fatty alcohol polyoxyethylene ether and 5g of acrylic acid were mixed and stirred evenly, 1.3g of p-toluenesulfonic acid and 0.04g of hydroquinone were added, and the vacuum degree was maintained at 0.03MPa. After reacting at 95°C for 7h, the vacuum degree was increased to remove unreacted acrylic acid to obtain fatty alcohol polyoxyethylene ether acrylate; A2. 25 g of fatty alcohol polyoxyethylene ether acrylate and 0.07 g of ammonium persulfate were added to 35 g of deionized water, stirred evenly, 9 g of maleic anhydride was added, stirred and reacted at 60 ° C for 20 min, cooled to room temperature, and 0.03 g of hydroquinone was added to stop the reaction to obtain modified fatty alcohol polyoxyethylene ether.

[0060] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.3 g of nano-silica to 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 0.7 g of γ-aminopropyltriethoxysilane and 6 mL of 30% sodium hydroxide solution, stir and react at 85 °C for 2 h, add 0.6 g of lignin, continue stirring and reacting for 2 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain lignin-modified nano-silica; B2. Add 3g aluminum chloride and 1g N,N,N',N'-tetraphenylbenzidine to 12mL dichloromethane, stir evenly, add 0.4g lignin-modified nano-silica, stir evenly, introduce nitrogen, stir at 1°C for 5h, stir at 35°C for 9h, stir at 45°C for 13h, stir at 65°C for 13h, stir at 85°C for 24h, add 2mL of 0.6mol / L hydrochloric acid solution to terminate the reaction, filter, wash 3 times with deionized water, wash 2 times with ethanol, extract with ethanol for 48h, and dry in an oven at 65°C for 24h to obtain a composite layered porous polymer; B3. Add 1.7 g of the composite layered porous polymer to 110 mL of deionized water, stir evenly, add 0.9 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.8 g of dopamine, stir and react at 40°C for 2 h, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 h to obtain an enhancer.

[0061] Comparative Example 5 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 50°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 50°C for aging for 2h, add isopropanol, stir evenly, add 35% sodium hydroxide solution by mass, and neutralize at 55°C for 2h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 50 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 55 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 60:10:10:20; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 80:15:8:0.7:4:15.

[0062] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 35g of fatty alcohol polyoxyethylene ether and 5g of acrylic acid were mixed and stirred evenly, 1.3g of p-toluenesulfonic acid and 0.04g of hydroquinone were added, and the vacuum degree was maintained at 0.03MPa. After reacting at 95°C for 7h, the vacuum degree was increased to remove unreacted acrylic acid to obtain fatty alcohol polyoxyethylene ether acrylate; A2. 25 g of fatty alcohol polyoxyethylene ether acrylate and 0.07 g of ammonium persulfate were added to 35 g of deionized water, stirred evenly, 9 g of maleic anhydride was added, stirred and reacted at 60 ° C for 20 min, cooled to room temperature, and 0.03 g of hydroquinone was added to stop the reaction to obtain modified fatty alcohol polyoxyethylene ether.

[0063] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.3 g of nano-silica to 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 0.7 g of γ-aminopropyltriethoxysilane and 6 mL of 30% sodium hydroxide solution, stir and react at 85 °C for 2 h, add 0.6 g of lignin, continue stirring and reacting for 2 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain lignin-modified nano-silica; B2. Add 3 g of lignin-modified nano-silica to 90 mL of deionized water, stir evenly, heat to 50 °C, add 10% sodium hydroxide solution to adjust the pH to 9, pass 0.4 mL of formaldehyde and 2 g of anhydrous sodium sulfite, stir and react for 4 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain sulfonated lignin-modified nano-silica; B3. Add 1.7 g of sulfonated lignin-modified nano-silica to 110 mL of deionized water, stir evenly, add 0.9 g of Tris-HCl buffer with a pH of 8.5, stir evenly, add 0.8 g of dopamine, stir and react at 40°C for 2 h, filter, collect the product, wash it twice with ethanol, and dry it in an oven at 70°C for 8 h to obtain an enhancer.

[0064] Comparative Example 6 A composite ionic surfactant is prepared by the following method: S1. Place vacuum residue in a reactor, stir and heat to 50°C, add sulfur trioxide for sulfonation reaction, stir and react until the temperature no longer rises, cool to 50°C for aging for 2h, add isopropanol, stir evenly, add 35% sodium hydroxide solution by mass, and neutralize at 55°C for 2h to obtain residue sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer were mixed, heated to 50 ° C, epoxidized soybean oil, linear heavy alkylbenzene sulfonic acid and water were added, stirring was continued for 55 min, the temperature was lowered and the material was discharged to obtain a composite ionic surfactant; Wherein, in step S1, the mass ratio of vacuum residue oil, sulfur trioxide, isopropanol and sodium hydroxide solution is 60:10:10:20; In step S3, the mass ratio of residual oil sulfonate, modified fatty alcohol polyoxyethylene ether, enhancer, epoxy soybean oil, linear heavy alkyl benzene sulfonic acid and water is 80:15:8:0.7:4:15.

[0065] The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. In a 150mL three-necked round-bottom flask equipped with a stirrer and a thermometer, 35g of fatty alcohol polyoxyethylene ether and 5g of acrylic acid were mixed and stirred evenly, 1.3g of p-toluenesulfonic acid and 0.04g of hydroquinone were added, and the vacuum degree was maintained at 0.03MPa. After reacting at 95°C for 7h, the vacuum degree was increased to remove unreacted acrylic acid to obtain fatty alcohol polyoxyethylene ether acrylate; A2. 25 g of fatty alcohol polyoxyethylene ether acrylate and 0.07 g of ammonium persulfate were added to 35 g of deionized water, stirred evenly, 9 g of maleic anhydride was added, stirred and reacted at 60 ° C for 20 min, cooled to room temperature, and 0.03 g of hydroquinone was added to stop the reaction to obtain modified fatty alcohol polyoxyethylene ether.

[0066] The reinforcing agent is specifically prepared by the following steps: B1. Add 1.3 g of nano-silica to 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 0.7 g of γ-aminopropyltriethoxysilane and 6 mL of 30% sodium hydroxide solution, stir and react at 85 °C for 2 h, add 0.6 g of lignin, continue stirring and reacting for 2 h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain lignin-modified nano-silica; B2. Add 3 g of lignin-modified nano-silica to 90 mL of deionized water, stir evenly, heat to 50 °C, add 10% sodium hydroxide solution to adjust the pH to 9, pass 0.4 mL of formaldehyde and 2 g of anhydrous sodium sulfite, stir and react for 4 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain sulfonated lignin-modified nano-silica; B3. Add 3g aluminum chloride and 1g N,N,N',N'-tetraphenylbenzidine to 12mL dichloromethane, stir evenly, add 0.4g sulfonated lignin-modified nano-silica, stir evenly, introduce nitrogen, stir at 1°C for 5h, stir at 35°C for 9h, stir at 45°C for 13h, stir at 65°C for 13h, stir at 85°C for 24h, add 2mL of 0.6mol / L hydrochloric acid solution to terminate the reaction, filter, wash 3 times with deionized water, wash twice with ethanol, extract with ethanol for 48h, and dry in an oven at 65°C for 24h to obtain an enhancer.

[0067] The performance of the composite ionic surfactants prepared in Examples 1-3 and Comparative Examples 1-6 was tested.

[0068] Formation water in Jin 45 block of North China Oilfield: mineralization is about 40,000 mg / L, calcium and magnesium ions are 700 mg / L.

[0069] The dehydrated and degassed crude oil from Jin 45 block in Huabei Oilfield has a density of 0.87 mg / L at the test temperature.

[0070] Interfacial tension test: The composite ionic surfactant prepared above was added into the formation water, the surfactant concentration was 0.2%, and the test instrument TX-500C rotating drop interfacial tension meter (SY / T5370-1999) was used for testing, the experimental temperature was 80°C, and the rotation speed was 5000r / min; Temperature resistance test: the composite ionic surfactant prepared above was added into formation water with a surfactant concentration of 0.2%, and placed in a constant temperature box at a formation temperature of 110°C for aging for 192 hours. After being taken out, the oil-water interfacial tension was tested; Displacement performance evaluation method: The end surface of the artificial core (core length 8.5 cm, inner diameter 2.3 cm) was ground flat and dried at 85°C; simulated oil configuration: degassed crude oil and dehydrated kerosene were evenly mixed in a volume ratio of 1:1; the artificial core was displaced with simulated oil to create bound saturated oil, and the volume of water V1 was recorded when the artificial core was displaced with a composite ionic surfactant with a concentration of 0.2%. The volume of oil displaced by formation water V2 was recorded; oil displacement efficiency of oil displacing agent (%) = V2 / V1×100%, V1 is the volume of reservoir oil in the artificial core (mL), and V2 is the volume of oil displaced by the oil displacing agent (mL).

[0071] The test results are shown in Table 1 below.

[0072] Table 1 Performance test of composite ionic surfactants prepared in Examples 1-3 and Comparative Examples 1-6

[0073] It can be seen from the data in Table 1 that the composite ionic surfactant prepared in Examples 1-3 has excellent salt resistance and high temperature resistance, and has a high crude oil recovery rate.

[0074] In Comparative Example 1, the modified fatty alcohol polyoxyethylene ether prepared by replacing fatty alcohol polyoxyethylene ether acrylate with fatty alcohol polyoxyethylene ether was added to the composite ionic surfactant, and its interfacial tension reduction performance and recovery rate decreased, proving that the reaction of fatty alcohol polyoxyethylene ether and acrylic acid is beneficial to improving the compatibility of non-ionic surfactant fatty alcohol polyoxyethylene ether with residual oil sulfonate, significantly reducing the oil-water interfacial tension and improving the displacement efficiency.

[0075] In Comparative Example 2, the modified fatty alcohol polyoxyethylene ether prepared without adding maleic anhydride was added to the composite ionic surfactant, and its interfacial tension reduction performance and recovery rate decreased, which proved that maleic anhydride was grafted on the fatty alcohol polyoxyethylene ether acrylate to improve the compatibility of fatty alcohol polyoxyethylene ether with residual oil sulfonate, and the carboxyl group contained in it could combine with the phenolic hydroxyl group in the enhancer to form a cross-linked network structure with steric hindrance, thereby improving salt resistance, temperature resistance and displacement efficiency.

[0076] In Comparative Example 3, the enhancer prepared without adding γ-aminopropyltriethoxysilane was added to the composite ionic surfactant, and its interfacial tension reduction performance and recovery rate decreased, proving that lignin was coated on the surface of nanoparticles through the coupling agent, with excellent temperature resistance and salt resistance, and was beneficial to the embedding of lignin-modified nano-silica into the porous polymer, thereby increasing the interlayer spacing and pore structure of the porous polymer, and improving the adsorption of polyvalent metal cations in the formation.

[0077] In Comparative Example 4, the enhancer prepared by replacing the sulfonated lignin-modified nano-silica with lignin-modified nano-silica was added to the composite ionic surfactant, which reduced the interfacial tension performance and the recovery rate, proving that the sulfomethylation treatment of the lignin-modified nano-silica improved the compatibility of the lignin-modified nano-silica with residual oil sulfonates, and the introduction of sulfonic acid groups further enhanced the adsorption of polyvalent metal cations in the formation.

[0078] In Comparative Example 5, the composite layered porous polymer is replaced with a reinforcing agent prepared by sulfonated lignin-modified nano-silica and added to the composite ionic surfactant. The interfacial tension performance and recovery rate are reduced, which proves that the mixed reaction of sulfonated lignin-modified nano-silica, biphenyl, catalyst and dichloromethane to form a composite layered porous polymer can increase the interlayer spacing of the layered porous network polymer, improve the adsorption of polyvalent metal cations in the formation, enhance the salt resistance and high temperature resistance of residual oil sulfonates, and thereby improve the oil recovery efficiency of the composite ionic surfactant.

[0079] In comparative example 6, the enhancer prepared by the composite layered porous polymer without modification with polydopamine was added to the composite ionic surfactant, and its interfacial tension reduction performance and recovery rate decreased, proving that the surface modification of the composite layered porous polymer with polydopamine further improved the adsorption of polyvalent metal cations in the formation, and was beneficial to the dispersion of the composite layered porous polymer in the residual oil sulfonate, thereby improving the salt resistance and temperature resistance of the composite ionic surfactant.

[0080] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0081] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A composite ionic surfactant, characterized in that: Prepared by the following method: S1. Vacuum residue oil and sulfur trioxide are mixed for sulfonation reaction. When the reaction temperature is no longer increased, aging is performed, isopropanol is added, stirred evenly, and sodium hydroxide solution is added for neutralization reaction to obtain residue oil sulfonate; S2. The fatty alcohol polyoxyethylene ether, acrylic acid and maleic anhydride are mixed and reacted to obtain a modified fatty alcohol polyoxyethylene ether; S3. The residual oil sulfonate, modified fatty alcohol polyoxyethylene ether and enhancer are mixed, heated to 40-50 ° C, a plasticizer, a linear heavy alkylbenzene sulfonic acid and water are added, stirring is continued for 45-55min, the temperature is lowered and the material is discharged to obtain a composite ionic surfactant; The reinforcing agent is obtained by mixing and reacting nanoparticles modified with sulfonated lignin, biphenyl, a catalyst and dichloromethane, and then surface-modifying with polydopamine; The sulfonated lignin modified nanoparticles are obtained by reacting lignin, a coupling agent and nanoparticles in a mixed manner, and then reacting the mixture with formaldehyde and anhydrous sodium sulfite for sulfomethylation.

2. A composite ionic surfactant according to claim 1, characterized in that: The modified fatty alcohol polyoxyethylene ether is specifically prepared by the following steps: A1. Mix fatty alcohol polyoxyethylene ether and acrylic acid, stir evenly, add p-toluenesulfonic acid and hydroquinone, maintain vacuum, react at 85-95 ° C for 5-7h, increase vacuum to remove unreacted acrylic acid, and obtain fatty alcohol polyoxyethylene ether acrylate; A2. Add fatty alcohol polyoxyethylene ether acrylate and ammonium persulfate to deionized water, stir evenly, add maleic anhydride, stir and react at 50-60°C for 10-20 minutes, cool to room temperature, add hydroquinone to stop the reaction, and obtain modified fatty alcohol polyoxyethylene ether.

3. A composite ionic surfactant according to claim 2, characterized in that: In step A1, the mass ratio of the fatty alcohol polyoxyethylene ether, acrylic acid, p-toluenesulfonic acid and hydroquinone is (25-35):(4-5):(1.1-1.3):(0.02-0.04).

4. A composite ionic surfactant according to claim 2, characterized in that: In step A2, the mass ratio of the fatty alcohol polyoxyethylene ether acrylate, ammonium persulfate, deionized water, maleic anhydride and hydroquinone is (25-35):(0.03-0.07):(25-35):(8-9):(0.01-0.03).

5. A composite ionic surfactant according to claim 1, characterized in that: The reinforcing agent is specifically prepared by the following steps: B1. Add the nanoparticles to ethanol and deionized water, stir evenly, add the coupling agent and sodium hydroxide solution, stir and react at 75-85°C for 1-2h, add lignin, continue stirring and reacting for 1-2h, cool to room temperature, filter, wash, and dry to obtain lignin-modified nanoparticles; B2. Add lignin-modified nanoparticles to deionized water, stir evenly, heat to 45-50°C, add sodium hydroxide solution to adjust the pH to 8-9, pass formaldehyde and anhydrous sodium sulfite, stir to react for 2-4h, cool to room temperature, filter, wash, and dry to obtain sulfonated lignin-modified nanoparticles; B3. Add the catalyst and biphenyl to dichloromethane, stir evenly, add the sulfonated lignin-modified nanoparticles, stir evenly, introduce nitrogen, stir at 0-1°C for 3-5h, stir at 25-35°C for 7-9h, stir at 35-45°C for 11-13h, stir at 55-65°C for 11-13h, stir at 75-85°C for 22-24h, add hydrochloric acid solution to terminate the reaction, filter, wash, extract, and dry to obtain a composite layered porous polymer; B4. Add the composite layered porous polymer to deionized water, stir evenly, add Tris-HCl buffer, stir evenly, add dopamine, stir and react at 30-40°C for 1-2h, filter, wash and dry to obtain an enhancer.

6. A composite ionic surfactant according to claim 5, characterized in that: In step B1, the ratio of the nanoparticles, ethanol, deionized water, coupling agent, sodium hydroxide solution and lignin is (1.1-1.3) g: (90-100) mL: (4-6) mL: (0.3-0.7) g: (4-6) mL: (0.4-0.6) g.

7. A composite ionic surfactant according to claim 5, characterized in that: In step B2, the ratio of the amount of the lignin-modified nanoparticles, deionized water, formaldehyde and anhydrous sodium sulfite is (2-3) g: (70-90) mL: (0.2-0.4) mL: (1.6-2) g.

8. A composite ionic surfactant according to claim 5, characterized in that: In step B3, the amount ratio of the catalyst, biphenyl, dichloromethane, sulfonated lignin-modified nanoparticles and hydrochloric acid solution is (2-3) g: (0.6-1) g: (8-12) mL: (0.2-0.4) g: (1-2) mL.

9. A composite ionic surfactant according to claim 5, characterized in that: In step B4, the ratio of the composite layered porous polymer, deionized water, Tris-HCl buffer and dopamine is (1.5-1.7) g: (90-110) mL: (0.7-0.9) g: (0.6-0.8) g.

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